Heterocyclic derivatives as flavoring agents

ABSTRACT

1,3-Oxathiane and 1,3-oxathiolane derivatives, some which are new, are disclosed as being useful as perfuming and flavoring agents for the preparation of perfumes and perfumed articles and for the manufacture of artificial flavors, flavored foodstuffs, animal feeds, beverages, pharmaceutical preparations and tobacco products.

CROSS-REFERENCE TO RELATED APPLICATION

This is a division of application Ser. No. 907,828, filed May 19, 1978, now U.S. Pat. No. 4,262,030, which in turn is a division of Ser. No. 805,338, filed June 10, 1977, now U.S. Pat. No. 4,220,561, which in turn is a continuation in part of Ser. No. 600,275, filed July 31, 1975, and now abandoned.

SUMMARY OF THE INVENTION

The present invention relates to the use of certain heterocyclic derivatives as flavouring and odoriferous agents. The said compounds, some of which are new, have the formula (I): ##STR1## in which: (a) m and n stand for zero or 1, and each of symbols R¹ to R⁸ represents a hydrogen atom or a saturated or unsaturated, linear or branched alkyl radical containing from 1 to 11 carbon atoms, or

(b) n stands for 1 and m represents zero or 1, each of symbols R¹, R², R³ and R⁴ have the above described meaning, R⁵ and R⁷ each represents hydrogen and R⁶ together with R⁸ and the carbon atoms carrying them, in positions 5 and 6 respectively, form a substituted or unsubstituted cyclopentane or cyclohexane ring, or

(c) n stands for 1 and m represents zero or 1, each of symbols R¹, R³, R⁵, R⁶ and R⁷ represents hydrogen, R² represents a lower alkyl radical or a hydrogen atom, R⁴ represents a para-substituted or unsubstituted phenyl or a substituted or unsubstituted cyclohexenyl radical, and R⁸ stands for a lower alkyl, or

(d) n stands for 1 and m represents zero or 1, each of symbols R¹, R³, R⁵, R⁶ and R⁷ represents hydrogen, R² a p-substituted or unsubstituted phenyl or a substituted or unsubstituted cyclohexenyl radical, R⁴ represents a lower alkyl radical or a hydrogen atom, and R⁸ stands for a lower alkyl or a hydrogen.

As indicated hereinabove R¹ to R⁸ can represent a saturated or unsaturated, linear or branched alkyl radical. Preferentially, R¹ to R⁸ each represents a methyl, ethyl, propyl, butyl, sec-butyl, ter-butyl, pentyl, hexyl, heptyl or octyl radical.

In paragraphs (c) and (d) above it is indicated that R² and R⁸ can represent a lower alkyl radical. They preferentially represent a methyl, ethyl or propyl radical.

In the above formula (I) the para-substituted phenyl groups represented by R⁴ or R², as the case may be, include, e.g., p-methyl-phenyl, p-ethyl-phenyl, p-propyl-phenyl, p-methoxy-phenyl and p-ethoxy-phenyl. Preferred para-substituted phenyl groups are p-methyl-phenyl and p-methoxy-phenyl.

R⁴ or R², as the case may be, can also represent a substituted or unsubstituted cyclohexenyl radical. Preferred cyclohexenyl radicals are cyclohex-3-enyl, 2,6,6-trimethyl-cyclohex-2-enyl, and 2,6,6-trimethyl-cyclohex-1-enyl. In the event that in formula (I) R⁶ together with R⁸ and the carbon atoms carrying them in positions 5 and 6 of the heterocyclic ring form a substituted cyclopentane or cyclohexane, the substituent can be, e.g. a lower alkyl radical such as methyl, ethyl or propyl. Methyl is a preferred substituent.

The compounds of formula (I) possess interesting organoleptic properties and accordingly, are useful as perfuming and odour-modifying agents, and as flavouring and taste-modifying agents. They can be compounded with other odoriferous substances to make perfumery compositions, in the manner conventional in the perfumery art; they can be used in combination with carriers or diluents, for perfuming a wide range of products; they can be used to modify, enhance or improve the organoleptic properties of foodstuffs, animal feeds, beverages, pharmaceutical preparations and tobacco products, and they can also be used in the manufacture of artificial flavouring compositions. Accordingly, the present invention consists in a composition comprising a compound of formula (I), as defined above, and a foodstuff, an animal feed, a beverage, a pharmaceutical preparation, a tobacco product, another odoriferous compound, or a perfume base.

This invention relates further to a method for modifying, improving or enhancing the organoleptic properties of foodstuffs, animal feeds, beverages, pharmaceutical preparations and tobacco products; as well as the odoriferous properties of perfumes and perfumed products, which method comprises adding thereto a small but effective amount of at least one compound of formula (I).

BACKGROUND OF THE INVENTION

The discovery of the utility of the compounds of formula (I) in the field of perfumery and flavours is particularly surprising. In their pure state in fact, these compounds develop a very powerful and unpleasant smell and it is only upon dilution that their odoriferous and flavouring properties become apparent.

The compounds of formula (I) belong to the class of derivatives known as 1,3-oxathianes (n=1) and 1,3-oxathiolanes (n=0). Their use, as well as that of their corresponding oxides (m=1), was hitherto unknown in perfumery and in the flavour art.

We have discovered 2-methyl-4-n-propyl-1,3-oxathiane and its corresponding oxide, viz. 2-methyl-4-n-propyl-1,3-oxathiane-3-oxide, as compounds of natural origin which can be isolated from an essential oil obtainable from the juice of the passion-fruit, Passiflora edulis flavicarpa. Passion-fruit juice is a commercial material available, for example, from Nationwide of Chicago, Food Brokers, Inc., 1400 Winston Plaza, Melrose Park, Ill., United States.

However, the procedure for isolating the said compounds from natural passion-fruit juice is extremely complex and uneconomical. The yield of essential oil obtained is not higher than 0.0012% by weight of the total juice treated. In order to isolate the above mentioned compounds, the juice is subjected to a preliminary distillation, by means of a special technique known as "thin layer distillation"--vide Helv. Chim. Acta, 45, 2186 (1962). This operation yield 18% by weight of an aqueous distillate from which the desired essential oil can be obtained by extraction with ethyl chloride followed by evaporation of the volatile components. The oil is then separated by column chromatography on silicic acid, by the procedure described in J. Chromatography 34, 174 (1968); and the polar fractions are then subjected to repeated separations by preparative gas chromatography to isolate the pure oxathiane derivatives.

Analytical and synthetic studies confirmed that these products were compounds of previously unknown structure.

The disadvantages and difficulties inherent in the isolation of 2-methyl-4-n-propyl-1,3-oxathiane and 2-methyl-4-n-propyl-1,3-oxathiane-3-oxide from the essential oil obtained from passion-fruit have been overcome by the discovery of a process for synthetically preparing these and the other compounds of formula (I). A particularly valuable feature of the synthetic process is that it readily yields the pure compounds, which have powerful organoleptic characteristics that are stable and perfectly reproducible; whereas, in contradistinction, the properties of the natural essential oil vary with the origin of the fruit from which it has been extracted, the method of extraction, and the purity of the essential oil recovered. Consequently, the synthetic compounds are useful as flavouring and perfuming ingredients over a wider field of application than the natural essential oil.

2-Isopropyl-1,3-oxathiolane and its phenyl analogue have been described by Kipnis et al. J.Am.Chem.Soc., 71, 3555 (1949) as liquids with fresh, aromatic aromas. In actual experience the compounds of the invention possess organoleptic properties which are by far, more superior than those described by Kipnis. The following Tables show the results of flavour evaluations carried out on 2-methyl-4-propyl-1,3-oxathiane in comparison with 2-isopropyl-1,3-oxathiolane and 2-phenyl-1,3-oxathiolane.

    ______________________________________                                         Evaluation in water                                                            Ingredient   Level      Evaluation                                             ______________________________________                                         1.  2-Methyl-4-   0.1 ppm   Sweet, green, fruity                                   propyl-1,3-             typical Passion-fruit                                  oxathiane                                                                      (100%)                                                                          ##STR2##    0.10 ppm   Strong alliaceous note, Cabbage, gas, burnt.                                   Rotten egg.                                             ##STR3##    0.20 ppm   Weaker than 1, less fruity. Woody, floral.                                     Slight egg character                               ______________________________________                                    

    ______________________________________                                         Evaluation in acidified sugar syrup*                                           Ingredient   Level        Evaluation                                           ______________________________________                                         1.  2-Methyl-4-  0.10 ppm     Fruity, juicy.                                       propyl-1,3-               Typical Passion-fruit.                               oxathiane                 Blackcurrant.                                        (100%)                                                                          ##STR4##    0.10 ppm     Lacks fruit juicy cha- racter. Burnt, gas                                      top note. Alliaceous.                                 ##STR5##    0.20 ppm     Less fruity than 1. Woody,                                                     floral. Vegetable character.                     ______________________________________                                          *10 g of a 50% aqueous solution of citric acid in a syrup containing 600       of sucrose per liter water.                                              

    ______________________________________                                         As reinforcer for natural Passion-fruit                                        Juice - Comparison made with unflavoured                                       juice.                                                                         Ingredient   Level     Evaluation                                              ______________________________________                                         1.  2-Methyl-4-  0.10 ppm  Enhanced juicy character.                               propyl-1,3-            Fresher top note.                                       oxathiane              Typical.                                                (100%)                                                                          ##STR6##    0.10 ppm  Burnt, alliaceous, Coffee. Not recognizable.                                   Direction Durian.                                        ##STR7##    0.20 ppm  Green vegetable character. Cooked, fatty. Not                                  typical.                                            ______________________________________                                    

Concerning its olfactive properties, 2-methyl-4-propyl-1,3-oxathiane is clearly distinguishable from the above cited oxathiolane derivatives described by Kipnis. 2-Isopropyl-1,3-oxathiolane possesses an extremely powerful almost unbearable smell in its pure state. Upon dilution the same compound developed a strong odour reminiscent of rotten grass and sewage with a "carbide" by-note. 2-Phenyl-1,3-oxathiolane showed a slight spicy-green character and a vague odour reminiscent of bitter almonds with a slight rotten smell. On the contrary, 2-methyl-4-propyl-1,3-oxathiane develops in a 1% by weight solution in diethyl-phthalate a pleasant scent having a fruity-green and fresh character reminiscent of the odour developed by blackcurrent shrub leaves.

Several oxathiane and oxathiolane derivatives have been reported in the past in the scientific literature. 2-(3-Heptyl)-1,3-oxathiolane and 2-(3-amyl)-1,3-oxathiolane have been described in U.S. Pat. No. 3,025,214. Pasto et al. [J.Am.Chem.Soc., 89, 4368 (1967)] have prepared various 1,3-oxathianes which may be alkylated in the 2-position. Van Acker et al. [Tetrahedron Letters 1974, 225-8] and Stevenson [J.Am.Chem.Soc., 96, 1067 (1974)] have described 1,3-oxathiane-5-oxides and 2-t-butyl-1,3-oxathiolanes, respectively. Djerassi et al. [J.Am.Chem.Soc., 75, 3704 (1953)], Rondestvedt [J. Org. Chem. 26, 2247 (1961)], De Wolf et al. [Tetrahedron Letters, 1970 551-4], Pihlaja et al. [Acta Chem. Scand. 1970, [24], 2257] and Pasanen et al. [Acta Chem. Scand. 1971, [25] 1908] showed a variety of 1,3-oxathianes which may be substituted in the 2-and the 6-positions.

None of the above cited references describes or even suggests the possibility of using the oxathiane or oxathiolane derivatives of the present invention as flavour or perfume ingredients and, what is more, no mention appears therein of the organoleptic properties of the described compounds, most of the cited authors having in fact limited their investigations to pure theoretical physicochemical studies.

PREFERRED EMBODIMENTS OF THE INVENTION

Specific examples of the compounds defined by structural formula (I) include the following:

1. 1,3-oxathiolane

2. 2-methyl-1,3-oxathiolane

3. 5-methyl-1,3-oxathiolane

4. 2,2-dimethyl-1,3-oxathiolane

5. 2,4-dimethyl-1,3-oxathiolane

6. 2,5-dimethyl-1,3-oxathiolane

7. 2,2,4-trimethyl-1,3-oxathiolane

8. 2-pentyl-1,3-oxathiolane

9. 2-pentyl-5-methyl-1,3-oxathiolane;

10. 1,3-oxathiane

11. 2-methyl-1,3-oxathiane

12. 2,2-dimethyl-1,3-oxathiane

13. 4,4,6-trimethyl-1,3-oxathiane

14. 2,4,4,6-tetramethyl-1,3-oxathiane

15. 2-ethyl-4,4,6-trimethyl-1,3-oxathiane

16. 2-propyl-4,4,6-trimethyl-1,3-oxathiane

17. 4-propyl-1,3-oxathiane

18. 2-methyl-4-propyl-1,3-oxathiane

19. 2,2-dimethyl-4-propyl-1,3-oxathiane

20. 2-methyl-2-ethyl-4-propyl-1,3-oxathiane

21. 2-methyl-2,4-dipropyl-1,3-oxathiane

22. 2-ethyl-4-propyl-1,3-oxathiane

23. 2-ter-butyl-4-propyl-1,3-oxathiane

24. 2-pentyl-4-propyl-1,3-oxathiane

25. 2-(pent-1-enyl)-4-propyl-1,3-oxathiane

26. 2-methyl-2-hexyl-4-propyl-1,3-oxathiane

27. 2-octyl-4-propyl-1,3-oxathiane

28. 2-undecyl-4-propyl-1,3-oxathiane

29. 2-methyl-4-heptyl-1,3-oxathiane

30. 2,2-dimethyl-4-heptyl-1,3-oxathiane

31. 2-ethyl-4-heptyl-1,3-oxathiane

32. 2-pentyl-4-heptyl-1,3-oxathiane

32b. 2-methyl-6-propyl-1,3-oxathiane

32c. 2,4,4,6-tetramethyl-2-propyl-1,3-oxathiane

33. 4-(cyclohex-3-en-1-yl)-6-methyl-1,3-oxathiane

34. 2,6-dimethyl-1,4-(cyclohex-3-en-1-yl)-1,3-oxathiane;

35. 4-(2,2,6-trimethyl-cyclohex-5-en-1-yl)-6-methyl-1,3-oxathiane

36. 2,6-dimethyl-4-(2,2,6-trimethyl-cyclohex-5-en-1-yl)-1,3-oxathiane

37. 2,6-dimethyl-4-(2,2,6-trimethyl-cyclohex-6-en-1-yl)-1,3-oxathiane

38. 4-(2,2,6-trimethyl-cyclohex-6-en-1-yl)-6-methyl-1,3-oxathiane

39. 2-(2,2,6-trimethyl-cyclohex-5-en-1-yl)-4-methyl-1,3-oxathiane

40. 4-phenyl-6-methyl-1,3-oxathiane

41. 4-(p-methyl-phenyl)-6-methyl-1,3-oxathiane

42. 2,6-dimethyl-4-(p-methyl-phenyl)-1,3-oxathiane

43. 4-(p-methoxy-phenyl)-6-methyl-1,3-oxathiane

44. 2,6-dimethyl-4-(p-methoxy-phenyl)-1,3-oxathiane

45. 5-butyl-2-oxa-4-thiabicyclo[4.3.0]nonane

46. 3-methyl-5-butyl-2-oxa-4-thiabicyclo[4.3.0]nonane

47. 5,5,9-trimethyl-2-oxa-4-thiabicyclo[4.4.0]decane

48. 2,5,5,9-tetramethyl-2-oxa-4-thiabicyclo[4.4.0]decane

49. 5,5,9-trimethyl-3-ethyl-2-oxa-4-thiabicyclo[4.4.0]decane

50. 5,5,9-trimethyl-3-propyl-2-oxa-4-thiabicyclo[4.4.0]decane

51. 3,5,5,9-tetramethyl-3-propyl-2-oxa-4-thiabicyclo[4.4.0]decane

52. 1,3-Oxathiane-3-oxide

53. 2-methyl-1,3-oxathiane-3-oxide

54. 2,2-dimethyl-1,3-oxathiane-3-oxide

55. 4-propyl-1,3-oxathiane-3-oxide

56. 2-methyl-4-propyl-1,3-oxathiane-3-oxide

57. 2-pentyl-4-propyl-1,3-oxathiane-3-oxide.

In the following Table the above compounds are listed together with their physical properties. Whenever a compound is commercially available or has been previously described in the chemical literature, it will be identified by the abbreviations "c.a." (commercially available) or "p.k." (prior known), respectively. The temperatures are given in degrees centigrade and the abbreviations have the meaning common in the art.

In the above given list of compounds, whenever reference is made to alkyl substituents such as, e.g., "propyl" it is deemed to refer to the unbranched radical such as, e.g. "n-propyl".

                  TABLE                                                            ______________________________________                                         Pro-                                                                           duct                                                                           No.  Physical properties                                                       ______________________________________                                          1.  p.k.    Suomi Kemistilehti B (1970) 43, 143                                2.  p.k.    Suomi Kemistilehti B (1970) 43, 143                                3.  MS:     M.sup.+ = 104 (96); m/e: 89 (1), 74 (65), 60 (100), 41                         (99)                                                                   NMR:    1.4 (3H, d), 2.53 (1H, d/d), 3.08 (1H, d/d), 4.02                              (1H, m), 4.85 (2H, m) δ ppm                                      IR:     2970, 2930, 2860, 2640, 1055, 720 cm.sup.-1                        4.  p.k.    Synth. Commun. 4, 6 (1974)                                         5.  MS:     M.sup.+  = 118 (53); m/e: 103 (22), 85 (0.5), 74 (100),                        59 (48), 41 (89)                                                       NMR:    1.35 (3H, d), 1.58 (3H, d), 3.0-4.5 (3H, m), 5.25                              (1H, m) δ ppm                                                6.  p.k.    Tetrahedron 28, 3943 (1972)                                        7.  MS:     M.sup.+  = 132 (24); m/e: 117 (3), 99 (0.5), 88 (1), 74                        (100), 59 (25), 43 (50), 41 (70)                                       NMR:    1.39 (3H, d), 1.62 (3H, s), 1.67 (3H, s), 2.76 (1H,                            (d/d), 3.14 (1H, d/d), 4.36 (1H, m) δ ppm                        IR:     2970, 2920, 2860, 2630, 1090, 590 cm.sup.-1                        8.  MS:     M.sup.+  = 160 (7); m/e: 89 (100), 60 (48), 61 (45), 45                        (9)                                                                    NMR:    0.88 (3H, t), 3.0 (2H, d/d), 3.76 (1H, d/d/d), 4.35                            1H, d/t), 5.08 (1H, t) δ ppm                                     IR:     2955, 2925, 2855, 2720, 1070, 658 cm.sup.-1                        9.  MS:     M.sup.+  = 174 (8.5); m/e: 127 (2), 115 ( ), 103 (100),                        83 (2), 74 (72), 55 (64), 41 (62).                                     NMR:    0.90 (3H, t), 1.40 (3H, d), 2.61 (1H, d/d), 3.09                               (1H, d/d), 4.18 (1H, m), 5.15 (1H, t) δ ppm                      IR:     2950, 2915, 2850, 2620, 1090, 655 cm.sup.-1                       10.  p.k.    Acta Chem. Scand. 24, 2257 (1970)                                 11.  p.k.    Acta Chem. Scand. 24, 2257 (1970)                                 12.  p.k.    Acta Chem. Scand. 24, 2257 (1970)                                 13.  B.p.    61°/11 Torr                                                     MS:     M.sup.+  = 146 (62), 131 (7.6), 113 (0.9), 102 (20.5), 87                      (35.3), 83 (16.1), 74 (31.7), 69 (10.7), 67 (7.6), 59                          (48.7), 56 (61.2), 43 (100), 41 (50.4)                                 NMR:    (60 MHz; CDCl.sub.3): 1.12-1.63 (5H, m), 1.26 (6H, s),                         3.40-3.92 (1H, sext.), 4.63-5.10 (2H, d of d) δ ppm         14.  B.p.    65°/15 Torr                                                     MS:     M.sup.+  = 160 (45.8), 145 (29.5), 132 (1.0), 116 (18.9),                      101 (41.5), 88 (12.1), 83 (42.1), 74 (72.1), 69                                (10.5), 67 (9.7), 61 (53.7), 60 (100), 59 (69.4), 55                           (34.2), 43 (32.1), 41 (45.8)                                           NMR     (60 MHz; CDCl.sub.3): 1.23 (6H, s); 1.15-1.55 (8H, m),                         3.47-4.06 (1H, sext.), 4.78-5.15 (1H, q) δ ppm              15.  B.p.    77°/13 Torr                                                     MS:     M.sup.+  = 174 (19.8), 145 (100), 116 (3.4), 101 (29.7),                       83 (84.5), 74 (80.7), 69 (12.6), 67 (8.2), 61 (42.5),                          60 (62.3), 59 (63.8), 55 (37.2), 43 (22.7), 41 (58.4)                  NMR     (60 MHz; CDCl.sub.3): 0.85-1.10 (3H, t), 1.25 (6H, s),                         1.12-1.95 (7H, m), 3.42-4.02 (1H, sext.), 4.67-4.87                            (1H, t) δ ppm                                               16.  B.p.    95°/13 Torr                                                     MS:     M.sup.+  = 188 (13.2), 145 (100), 116 (3.9), 101 (27.8),                       88 (12.8), 83 (76.7), 74 (50.7), 69 (11.4), 67 (6.4),                          61 (39.7), 60 (58.4), 59 (40.2), 55 (44.3), 43                                 (13.2), 41 (41.5)                                                      NMR     (60 MHz; CDCl.sub.3): 0.8-1.05 (3H, t), 1.25 (6H, s),                          1.15-1.90 (9H, m), 3.40-4.02 (1H, sext.), 4.70-4.97                            (1H, t) δ ppm                                               17.  MS:     M.sup.+  = 146 (50); m/e: 114 (27), 103 (95), 73 (100),                        55 (57), 45 (49)                                                       NMR:    0.92 (3H, t), -- 1.80 (2H, d/d), 3.02                                          (1H, bm), 3.52 (1H, m), 4.15 (1H, d/tr), 4.80 (2H,                             s) δ ppm                                                         IR:     2950, 2920, 2860, 2720, 1085, 575 cm.sup.-1                       18.  vide    p. 28 & 29 of this specification                                  19.  MS:     M.sup.+  = 174 (37); m/e: 159 (35), 116 (49), 101 (70),                        87 (100), 73 (55), 55 (98), 41 (76)                                    NMR:    0.90 (3H, tr), 1.47 (3H, s), 1.64 (3H, s), 3.12                                (1H, bm), 3.87 (2H, d/d) δ ppm                                   IR:     2960, 2925, 2870, 2720, 1080, 600 cm.sup.-1                       20.  MS:     M.sup.+  = 188 (3.5); m/e: 173 (6), 159 (100), 116 (19),                       101 (41), 83 (66), 73 (57), 55 (87), 43 (75)                           NMR:    0.95 (6H, m), 1.4 (6H, m), 1.6 (3H, s), 3.09 (1H,                              bm), 4.85 (2H, m) δ ppm                                          IR:     2960, 2920, 2865, 2720, 1080, 585 cm.sup.-1                       22.  MS:     M.sup.+  = 174 (13); m/e: 145 (100), 101 (8.5), 83 (24),                       73 (21), 55 (48), 41 (32)                                              NMR:    0.99 (6H, m), -- 2.99 (1H, bm), 3.65 (1H,                                      m), 4.22 (1H, d/tr), 4.64 (1H, tr) δ ppm                         IR:     2960, 2920, 2870, 2840, 2730, 1100, 1075, 575 cm.sup.-1           23.  MS:     M.sup.+  = 202 (2); m/e: 146 (100), 83 (27), 73 (5), 55                        (35), 41 (20)                                                          NMR:    1.0 (12H, bs), 1.4-1.9 (6H, m), 2.98 (1H, bm), 3.65                            (1H, m), 4.25 (1H, d/tr), 4.45 (1H, s) δ ppm                     IR:     2950, 2920, 2855, 2720, 1085, 640 cm.sup.-1                       24.  MS:     M.sup.+  = 216 (4); m/e: 145 (100), 117 (3), 101 (8), 83                       (28), 73 (13), 55 (42), 41 (26)                                        NMR:    0.89 (6H, bm), 3.0 (1b, bm), 3.62 (1H, m), 4.2 (1H,                            d/t), 4.7 (1H, t) δ ppm                                          IR:     2955, 2920, 2850, 2725, 1085, 660 cm.sup.-1                       25.  MS:     M.sup.+  = 214 (31); m/e: 185 (6), 171 (18.5), 145 (5.5),                      131 (2), 116 (22), 98 (60), 87 (70), 73 (47), 55                               (100), 41 (88).                                                        IR:     3040, 3015, 2960, 2880, 1665, 1075, 960                                        720 cm.sup.-1                                                     26.  MS:     M.sup.+  = 244 (0.5); m/e: 229 (1), 159 (42), 128 (4),                         116 (23.5), 101 (20), 87 (32), 73 (20), 58 (65),                               43 (100), 41 (46)                                                      NMR:    0.9 (6H, bm), 1.6 (3H, s), 3.16 (1H, bm), 3.89 (2H,                            m) δ ppm                                                         IR:     2940, 2910, 2850, 2720, 1085, 600 cm.sup.-1                       27.  MS:     M.sup.+  = 258 (2); m/e: 145 (100), 124 (2.5), 117 (4),                        101 (5), 87 (11), 83 (25), 69 (9.5), 55 (39), 41 (29),                         29 (92)                                                                NMR:    0.89 (6H, bm), 2.98 (1H, bm), 3.63 (1H, m), 4.2 (1H,                           d, t), 4.7 (1H, t) δ ppm                                         IR:     2950, 2915, 2845, 2720, 1085, 660 cm.sup.-1                       28.  MS:     M.sup.+  = 300 (--); m/e: 166 (2), 145 (100), 116 (5.5),                       101 (5.5), 83 (22), 69 (8.5), 55 (35), 41 (25)                         NMR:    0.91 (6H, bm), 2.97 (1H, bm), 3.7 (1H, m), 4.19                                (1H, d/t), 4.69 (1H, t) δ ppm                                    IR:     2940, 2910, 2835, 2720, 1095, 1075, 660 cm.sup.-1                 29.  MS:     M.sup.+  = 216 (43): m/e: 201 (57), 170 (78), 157 (2.5),                       143 (37), 129 (18), 115 (61), 101 (54), 87 (85), 73                            (65), 55 (100), 41 (80)                                                NMR:    0.89 (3H, t), 1.48 (3H, d), 1.7 (2H, m), 3.01 (1H,                             bm), 3.56 (1H, m), 4.2 (1H, d/t), 4.81 (1H, q)                                 δ ppm                                                            IR:     2950, 2920, 2850, 2720, 1095, 670 cm.sup.-1                       30.  MS:     M.sup.+  = 230 (4); m/e: 215 (8), 199 (--), 187 (0.5),                         172 (14), 157 (--), 143 (36), 129 (21), 115 (53),                              101 (47), 87 (87), 64 (45), 55 (80), 43 (100)                          NMR:    0.90 (3H, t), 1.52 (3H, s), 1.69 (3H, s), 3.12 (1H,                            bm), 3.92 (2H, m) δ ppm                                          IR:     2950, 2920, 2850, 2720, 1080, 595 cm.sup.-1                       31.  MS:     M.sup.+  = 230 (6.5); m/e: 216, (--), 201 (100), 185                           (0.5), 170 (3), 157 (0.5), 143 (2), 129 (1), 115                               (6.5), 97 (13), 83 (33), 69 (33), 55 (48), 41 (42)                     NMR:    0.99 (6H, m), 2.95 (1H, bm), 3.60 (1H, m), 4.18                                (1H, d/d), 4.61 (1H, t) δ ppm                                    IR:     2955, 2920, 2850, 2725, 1105, 1090, 720 cm.sup.-1                 32.  MS:     M.sup.+  = 272 (2); m/e: 201 (100), 182 (0.5), 170 (3),                        157 (0.5), 143 (5.5), 129 (4), 115 (11), 97 (11),                              83 (33), 69 (31), 55 (55), 41 (52)                                     NMR:    0.87 (6H, bt), 2.97 (1H, bm), 3.6 (1H, m), 4.16                                (1H, d/tr), 4.65 (1H, t) δ ppm                                   IR:     2950, 2920, 2850, 2720, 1090, 720 cm.sup.-1                       32b. B.p.    75°/9 Torr                                                      NMR:    0.92 (34.6), 1.46 (3H, d, J=6Hz), 1.2-1.9 (6H, m),                             2.5-3.2 (1H, m), 3.2-3.7 (1H, m), 4.89 (1H, q,                                 J=6Hz) δ ppm                                                     MS:     M.sup.+  = 160 (34), 87 (100), 41 (51), 60 (43), 67 (38),                      80 (36.5), 55 (35.5), 45 (33), 101 (21.5), 116 (21)               32c. B.p.    89°/11 Torr                                                     MS:     202 (1.7), 187 (3.3), 159 (77.6), 116 (36.0), 101                              (54.2), 87 (22.9), 83 (72.0), 74 (80.4), 69 (20.6),                            67 (10.3), 61 (66.8), 60 (94.4), 59 (64.9), 55                                 (38.3), 43 (100), 41 (26.2)                                            NMR     (90 MHz; CDCl.sub.3) 0.80-1.06 (3H, t), 1.25 (6H, s),                          1.15-1.90 (12H, m), 3.70-4.25 (1H, m) δ ppm                 33.  B.p.    73°/0.001 Torr                                                  MS:     M.sup.+  = 198 (10.5), 117 (100), 73 (81), 79 (50), 93                         (34), 45 (31.5), 41 (26.5), 87 (23), 53 (14), 67 (12),                 NMR:    1.2 (3H, d, J=6Hz), 1.4-2.4 (9H, m), 2.5-4.0                                   (2H, m), 4.87 (2H, s), 5.7 (2H, bs) δ ppm                   34.  B.p.    78°/0.001 Torr                                                  MS:     M.sup.+  = 212 (14), 79 (100), 93 (92), 80 (84), 87 (80),                      131 (76), 92 (66), 91 (55), 45 (52), 41 (47)                           NMR:    1.16 (1H, d), 1.22 (2H, d), 1.39 (1H, d), 1.46 (2H,                            d), 1.6-2.5 (9H, m), 2.7-4.0 (2H, m), 4.7-5.3 (1H,                             m), 5.7 (2H, s) δ ppm                                       35.  Isomer A - B.p. 100°/0.5 Torr                                      MS:      M.sup.+  = 240 (3.5), 73 (100), 117 (61), 87 (12),                             41 (12), 55 (5.7).                                                    NMR:     0.88 (3H, s), 1.08 (3H, s), 1.3 (3H, d, J=6Hz), 1.82                           (3H, m), 3.55 (1H, m), 4.25 (1H, bm), 4.54 (1H, d,                             J=11 Hz), 5.19 (1H, d, J=11Hz), 5.45 (1H, m) δ ppm              Isomer B - B.p. 100°/0.5 Torr                                                MS:     M.sup.+  = 240 (4), 73 (100), 117 (65), 41 (10.7), 87                          (10.4), 55 (5.5)                                                       NMR:    0.9 (3H, s), 1.09 (3H, s). 1.18 (3H, d, J=6Hz), 1.8                            (3H, m), 3.1-3.8 (2H, m), 4.87 (2H, s), 5.5 (1H, m)                            δ  ppm                                                      36.  B.P.    100°/0,5 Torr                                                   MS:     M.sup.+  = 254 (2), 87 (100), 131 (34), 45 (10), 41 (9),                       123 (4.6), 107 (4.4), 55 (4.1)                                         NMR:    0.88 (3H, s), 1.07 (3H, s), 1.2 (3H, d, J=6Hz),                                1.45 (3H, d, J=6Hz), 1.8 (3H, m), 3.1-3.8 (2H, m),                             4.85 (1H, q, J=6Hz) δ ppm                                   37.  B.p.    85°/0.05 Torr                                                   MS:     M.sup.+  = 254 (35), 41 (100), 135 (85), 107 (76), 43                          (71), 55 (71), 61 (71), 93 (69), 161 (67), 91 (62), 119                        (62), 121 (62), 69 (59), 167 (59), 79 (47)                             NMR:    0.99 (3H, s), 1.09 (3H, s), 1.24 (3H, d, J=6Hz),                               1.45 and 1.5 (3H, d, d, J=6Hz), 1.88 (3H, s), 3.3-                             4.2 (2H, m), 4.6-5.4 (1H, m) δ ppm                          38.  Isomer A - B.p. 95°/0.2 Torr                                       MS:      M.sup.+  = 240 (45.5), 135 (100), 43 (93), 91 (82), 149                        (75), 41 (72), 93 (70), 107 (61), 45 (47.5), 55                                (46.5), 69 (43), 79 (41), 81 (38.5), 121 (37.5)                       NMR:     1.0 (3H, s), 1.09 (3H, s), 1.2 (3H, d, J=6Hz), 1.88                            (3H, s), 3.3-3.8 (2H, m), 4.87 (2H, s) δ ppm                    Isomer B - B.p. 95°/0.2 Torr                                            MS:      M.sup.+  = 240 (33), 43 (100), 135 (98), 93 (80), 41 (77),                     95 (69), 149 (65), 107 (64), 121 (51), 55 (49), 69                             (43.5), 79 (42)                                                       NMR:     1.0 (3H, s), 1.12 (3H, s), 1.4 (3H, d, J=6Hz), 1.92                            (3H, s), 2.4-3.0 (1H, m), 3.8-4.4 (1H, m), 4.6 (1H,                            d, J=11Hz), 5.23 (1H, d, J=1Hz) δ ppm                           39.  Isomer A - B.p. 110°/0.1 Torr                                      MS:      M.sup.+  = 240 (4.7), 75 (100), 117 (85), 123 (76), 41                         (69), 81 (50), 107 (40), 43 (39.5), 93 (36.5), 45                              (36.5), 55 (35), 69 (33)                                              NMR:     0.87 (3H, s), 0.95 (3H, s), 1.23 (3H, d, J=6Hz),                               1.81 (3H, s), 2.5-3.9 (2H, m), 4.86 (2H, d, J=2Hz),                            5.53 (1H, m) δ ppm                                              Isomer B - B.p. 110°/0.1 Torr                                                MS:     M.sup.+  = 240 (4.3), 75 (100), 117 (79), 123 (71), 41                         (38), 81 (38), 43 (28), 210 (19), 107 (18.5)                           NMR:    0.9 (3H, s), 1.0 (3H, s), 1.24 (3H, d, J=6Hz), 1.8                             (3H, m), 2.5-3.7 (2H, m), 4.86 (2H, s), 5.5 (1H, m)                            δ ppm                                                       40.  B.p.    80°/0.1 Torr                                                    MS:     M.sup.+  = 194 (31), 104 (100), 43 (51), 121 (43), 122                         (42), 91 (26), 161 (21), 77 (21), 45 (18)                              NMR:    1.23 (1.3H, D, J=6Hz), 1.24 (1.7H, d, J=6Hz),                                  1.7-2.3 (2H, m), 3.2-4.4 (2H, m), 4.87 (0.8H, s),                              4.93 (1.2H, s), 7.29 (5H, m) δ ppm                          41.  B.p.    140°/0.01 Torr                                                  MS:     M.sup.+  = 208 (37), 118 (100), 43 (60), 117 (39), 135                         (37), 136 (35), 105 (35), 91 (34)                                      NMR:    1.25 (3H, d, J=6Hz), 2.32 (3H, s), 3.3-4.5 (2H, m),                            4.9 (0.7H, s), 4.98 (1.3H, s), 7.22 (4H, m) δ ppm           42.  B.p.    100°/0.001 Torr                                                 MS:     M.sup.+ = 222 (40), 136 (100), 135 (58), 118 (55), 145                         (38), 91 (34), 163 (31.5), 105 (26), 43 (24)                           NMR:    1.15 (3H, d, J=6Hz), 1.45 (3H, d, J=6Hz), 2.31 (3H,                            s), 3.7 (1H, m), 4.22 (1H, m), 5.0 (1H, m) δ ppm            43.  B.p.    100°/0.01 Torr                                                  MS:     M.sup.+  = 224 (50), 134 (100), 135 (98), 121 (94), 136                        (78), 43 (72), 147 (46), 91 (39), 77 (39), 45 (35)                     NMR:    1.25 (3H, d, J=6Hz), 1.5-2.0 (2H, m), 3.3-4.3                                  (2H, m), 3.77 (3H, s), 4.96 (2H, s), 6.8-7.4                                   (4H, m) δ ppm                                               44.  B.p.    110°/0.01 Torr                                                  MS:     M.sup.+  = 238 (47), 152 (100), 161 (75), 134 (62), 43                         (33), 121 (31), 91 (28), 204 (17), 65 (16), 77 (16)                    NMR:    1.16 (3H, d, J=6Hz), 1.3-1.6 (3H, m), 3.5-4.0 (1H                              m), 3.79 (1H, s), 3.8 (2H, s), 4.27 (1H, t), 4.8-5.3                           (1H, m), 6.8-7.6 (4H, m) δ ppm                              45.  B.p.    73°/0.01 Torr                                                   MS:     M.sup.+ = 200 (42), 67 (100), 41 (97), 168 (62), 110                           (60), 81 (60), 55 (56), 95 (47), 143 (36)                              NMR:    0.9 (3H, t), 1.2-2.1 (13H, m), 3.4 (1H, m), 3.83                               (1H, s), 4.72 (1.6H, s), 4.9 (0.4H, s) δ ppm                46.  B.p.    66°/0.01 Torr                                                   MS:     M.sup.+ = 214 (43), 67 (100), 95 (86), 81 (81), 41 (79),                       101 (58), 60 (57), 168 (43), 114 (40), 55 (38), 87                             (37)                                                                   NMR:    0.1 (3H, t), 1.43 (3H, d), 3.4 (1H, bm), 3.9 (1H,                              bs), 4.25 (1H, q) δ ppm                                     47.  B.p.    118°/12 Torr                                                    MS:     M.sup.+  = 200 (74.3), 185 (19.6), 167 (2.3), 154 (23.7),                      139 (20.5), 137 (19.6), 136 (15.6), 121 (31.8), 112                            (29.1), 111 (28.6), 110 (22.3), 109 (33.2), 95 (59.1),                         81 (77.3), 75 (100), 74 (59.5), 69 (73.6), 67 (32.7),                          59 (29.5), 55 (55.9), 53 (21.8), 43 (30.0), 41 (89.8)                  NMR:    0.70-1.08 (5H, m), 1.10-1.32 (4H, s), 1.40-2.15 (8H,                           m), 3.83- 4.05 (1H, m), 4.60-5.17 (2H, q) δ ppm             48.  B.p.    113°/13 Torr                                                    MS:     M.sup.+  = 214 (59.4), 199 (48.9), 170 (52.8), 155 (24.4),                     137 (81.1), 128 (43.3), 127 (41.67), 117 (26.7), 109                           (20.6), 95 (100), 81 (99.3), 75 (89.4), 74 (62.8),                             69 (55.0), 67 (40.0), 59 (40.6), 55 (62.2), 41 (98.9)                  NMR:    0.75-1.25 (12H, m), 1.40-2.10 (8H, m), 3.86-4.08                               (1H, m), 4.80-5.18 (1H, q) δ ppm                            49.  B.p.    110°/13 Torr                                                    MS:     M.sup.+  = 228 (10.7), 199 (67.6), 170 (7.1), 155 (6.9),                       137 (100), 128 (14.8), 127 (15.3), 121 (14.3), 109                             (9.3), 95 (54.9), 81 (62.6), 75 (31.9), 74 (26.6),                             69 (26.9), 67 (23.1), 59 (15.4), 55 (34.6), 41 (59.9)                  NMR:    0.7-1.20 (12H, m), 1.50-2.10 (10H, m), 3.85-4.05                               (1H, m), 4.70-4.85 (1H, t) δ ppm                            50.  B.p.    56°/0.15 Torr                                                   MS:     M.sup.+  = 242 (7.4), 199 (67.3), 170 (6.9), 155 (6.5),                        152 (4.1), 137 (100), 128 (13.8), 127 (14.3), 121                              (9.2), 109 (8.8), 95 (44.2), 81 (53.5), 75 (27.6),                             74 (19.8), 69 (22.1), 67 (19.4), 59 (12.4), 55 (34.1)                          43 (18.0), 41 (43.8)                                                   NMR:    0.70-1.25 (12H, m), 1.39-2.15 (12H, m), 3.85-4.05                              (1H, m), 4.75-5.05 (1H, t) δ ppm                            51.  B.p.    146°/14 Torr                                                    MS:     M.sup.+  = 256 (0.9), 241 (6.5), 213 (43.3), 170 (36.8),                       155 (9.5), 137 (83.6), 128 (23.9), 127 (23.6), 109                             (19.9), 95 (88.6), 81 (82.1), 75 (32.8), 74 (26.9),                            69 (34.3), 67 (44.8), 59 (18.9), 55 (44.8), 53                                 (20.9), 43 (100), 41 (76.1)                                            NMR:    0.75-1.24 (12H, m), 1.40-2.05 (15H, m), 4 -4.30                                (1H, m) δ ppm                                               52.  MS:     M.sup.+  = 120 (<1); m/e: 90 (76), 73 (17), 42 (29), 41                        (100)                                                                  NMR:    1.45-3.55 (4H, bm), 3.83 (2H, t), 4.42 (1H, d, d),                             4.80 (1H, d, d) δ ppm                                            IR:     2960, 2910, 2850, 2730, 1095, 1050, 830 cm.sup.-1                 53.  MS:     M.sup.+  = 134 (<1); m/e: 90 (86), 73 (22), 45 (24), 43                        (37), 41 (100)                                                         IR:     2960, 2910, 2860, 2725, 1110, 1045, 865, 835 cm.sup.-1            54.  MS:     M.sup.+  = 148 (7); m/e: 130 (26), 90 (100), 73 (29), 61                       (44), 59 (46), 43 (94), 41 (86)                                        IR:     2980, 2925, 2870, 2720, 1080, 1060, 1040, 855 cm.sup.-1           55.  MS:     M.sup.+  = 162 (<1); m/e: 132 (53), 89 (46), 83 (38), 77                       (24), 55 (100), 41 (47)                                                IR:     2950, 2925, 2870, 2725, 1105, 1045, 860 cm.sup.-1                 56.  vide    p. 31 of this specification                                       57.  MS:     M.sup.+  = 232 (0); m/e: 145 (100), 87 (18), 83 (42), 67                       (17), 55 (69), 45 (18), 43 (23), 41 (53)                          ______________________________________                                    

Depending upon the nature of the other constituents in compositions to which they are added, the compounds of formula (I) can develop various odoriferous or gustative notes such as fruity, green, alliaceous, caramel-like or slightly burnt and rubbery notes.

These organoleptic characteristics render the compounds of formula (I) particularly suitable for the aromatization of beverages such as fruit juices, syrups, vegetable juices or coffee drinks and soups or for the aromatization of tobacco products.

When the compounds of formula (I) are used as perfuming ingredients, they can develop upon dilution powerful and natural fruity type fragrances.

The term "foodstuff" is used broadly and includes, for example, coffee, tea or chocolate. The term "tobacco" includes natural tobacco and tobacco substitutes, whether of natural or synthetic origin, intended for smoking in pipes, cigars or cigarettes, for chewing, or for use as snuff.

The concentration at which the compounds of formula (I) can be used as flavouring agents, in accordance with the invention, can vary widely, depending upon the specific organoleptic effect desired and the type of material to which they are added. Typically, interesting flavouring effects can be achieved with amounts ranging from 0.01 to 100 ppm (parts per million) by weight of the flavoured material.

Preferentially, this concentration is comprised between about 0.01 and 10 ppm. The compounds of formula (I) in which m is 1, viz. the oxide derivatives, can be used at concentrations of about 0.1-50 ppm. The effects achieved by the use of these oxides is particularly interesting as they enhance the natural character of the fruity note of the materials to which they are added. Their effect, though, is less markedly characteristic than that achieved by the corresponding oxathianes or oxathiolanes compounds; specifically, they are less powerful than these compounds.

When used as perfuming ingredients, the compounds of formula (I) can be used at concentrations which typically are on the order of 0.01% by weight based on the total weight of the perfuming composition in which they are incorporated. Preferential concentrations range from about 0.01 to 0.1 %. The compounds of formula (I) can be used alone or in compositions containing one or more other flavouring or odoriferous componds, in diluted or concentrated solutions in solvents conventionally employed for flavouring and perfumery, for example ethyl alcohol, triacetin, diethylene-glycol and diethyl phthalate.

Among the compounds listed above, the following possess especially interesting organoleptic properties:

2-methyl-4-propyl-1,3-oxathiane,

4-propyl-1,3-oxathiane,

2,2-dimethyl-4-propyl-1,3-oxathiane,

2-ethyl-4-propyl-1,3-oxathiane,

2-pentyl-4-propyl-1,3-oxathiane,

4-(2,2,6-trimethyl-cyclohex-5-en-1-yl)-6-methyl-1,3-oxathiane

and 5-butyl-2-oxa-4-thiabicyclo[4.3.0.]nonane, together with their corresponding 3-oxide derivatives, namely the 2-methyl-4-propyl-1,3-oxathiane-3-oxide.

The compounds of formula (I), in which m is zero, can be obtained by a process which comprises reacting a thiol-alcohol of formula (II): ##STR8## (in which symbols R³ to R⁸ and index n have the aforementioned meaning) with a carbonyl compound of formula (III): ##STR9## (in which R¹ and R² have the meaning described above) in the presence of an acid catalyst.

The sulphur compounds of formula (II), used as starting materials in the process described above, can be obtained by a process which consists (a) in reacting hydrogen sulphide and the desired unsaturated carboxylic acid or, if desired, one of its corresponding esters and (b) reducing or hydrolizing, respectively, the sulphur addition compound thus obtained.

The alcohols of formula (II) can also be prepared by reducing the corresponding aldehydes, e.g. according to the procedure described in German Patent Application DOS No. 2,338,680.

In the preparation of the compounds of formula (I), carbonyl derivatives (III) can be replaced by their corresponding ketal or acetal derivatives.

Typically, the compounds of formula (I) were prepared in accordance with the following method:

A mixture of 1.34 g (10 mM) of 3-mercapto-hexanol, 2.2 g (50 mM) of acetaldehyde and 20 ml of cyclohexane were refluxed in the presence of a few milligrams of p-toluenesulphonic acid in a reaction vessel equipped with a water separator device. The reaction was over in about 30 minutes as indicated by the total recovery of the theoretical amount of water formed. The residue was successively washed with a 10% aqueous NaHCO₃ solution and water. The aqueous phase was extracted with ether (2 fractions) and the ethereal layers thus separated were concentrated to yield 1.5 g of a residue which on distillation gave a fraction having b.p. 82°-5°/10 Torr; n_(D) =1.4790; d₄ ²⁰ =0.9703.

IR (neat): 2940, 2905, 2804, 2700, 1083, 664 cm⁻¹.

NMR (CDCl₃ ; 90 MHz): 0.95 (3H); 1.5 (3H, d); 1.5 (6H, m); 3.08 (1H, m); 3.58 and 4.20 (2H, m); 4.8 (1H, q) δ ppm.

The material obtained essentially consisted of a mixture of two stereoisomers, defined as cis and trans, in a weight ratio of about 9:1, respectively. Consequently, 2-methyl-4-propyl-1,3-oxathiane is better represented by the following formula: ##STR10## which in turn indifferently defines one or the other of the compounds of formula: ##STR11##

Moreover, each of the above indicated epimers can occur in a racemic form or in the form of one of its enantiomers. This applies equally well to all the compounds of formula (I).

These isomers could be separated by means of vapour phase chromatography by using a 20 M CARBOWAX column. The compounds obtained were characterized by the following physical data:

Isomer A

MS: M⁺ =160 (64.5); M+2⁺ (2.5); m/e: 145 (67.5); 116 (13); 101 (51); 87 (82.5); 73 (71.5); 60 (58); 55 (100); 45 (72); 41 (72); 41 (66.5).

Isomer B

MS: M⁺ =160 (62); M+2⁺ (2.5); m/e: 145 (65); 116 (12.5); 101 (48); 87 (78.5); 73 (75); 60 (62.5); 55 (100); 45 (78); 41 (62).

For all practical purposes and in accordance with the invention, the mixture obtained in accordance with the above described method can satisfactorily be employed. However, especially for their use in perfumery, the two isomers can be separated and individually used for perfume compounding, the cis isomer being preferred.

3-Mercapto-hexanol, used as starting material in the above described process, can be synthetized according to the procedure described in Houben-Weyl, Methoden der Organischen Chemie 9, 21 (1955), or in Acta Chem. Scand. 25, 1908 (1971). This alcohol had the following analytical data:

B.p. 45°/0.001 Torr; n_(D) =1.4796; d₄ ²⁰ =0.9744.

Typically, the alcohol is prepared as follows:

(a) 8.36 g (0.11 M) of thio-acetic acid were added dropwise to 9.8 g (0.1 M) of hex-1-en-3-one while the reaction temperature increased to 50°. After 1 h stirring at that temperature, 3-oxo-hexyl thioacetate was recovered at b.p. 111°-3°/10 Torr.

(b) 15.6 g (0.09 M) of the said thioacetate in 50 ml of anhydrous ether was added slowly to a suspension of 3.8 g (0.1 M) of LiAlH₄ in 100 ml ether in a nitrogen atmosphere. Once the addition was over, the reaction mixture was refluxed during 1 h, then it was cooled to 0° and the excess of LiAlH₄ was decomposed by slow addition of 10 ml of water followed by 200 ml of 10 % HCl. After separation, the ethereal phase was washed with water, dried over MgSO₄ and concentrated. A distillation over a Vigreux column afforded the desired thio-alcohol in 85% yield.

Alternatively, the alcohols of formula (II) can be synthesized by reacting an α,β-unsaturated ketone with thio-acetic acid as follows:

(a') 0.11 M of thio-acetic acid were added dropwise to 0.1 M of the α,β-unsaturated ketone of formula ##STR12## The reaction mixture was then heated for a time period ranging from about 1 to 6 h at a temperature of about 50°-105°.

(b') The reduction of the obtained thio-acetate into its corresponding thio-alcohol was carried out by means of LiAlH₄ as indicated sub letter (b).

The compounds of formula (I) in which index m is 1, can be prepared by oxidizing the oxathianes or oxathiolanes of formula (I), in which m is zero, by conventional techniques. Thus 2-methyl-4-propyl-1,3-oxathiane-3-oxide, e.g., was prepared by oxidizing 2-methyl-4-propyl-1,3-oxathiane by means of H₂ O₂ according to the procedure described in J. Am. Chem. Soc. 90, 309 (1968) or by means of perbenzoic acid, m-chloro-perbenzoic acid-vide: Houben-Weyl, IX, Georg Thieme Verlag, 213 (1955)-, or m-periodic acid-vide; J. Org. Chem. 27, 282 (1962)-.

Typically, 2-methyl-4-propyl-1,3-oxathiane-3-oxide could be prepared as follows:

40 mMoles of 2-methyl-4-propyl-1,3-oxathiane were dissolved in 20 ml of CH₂ Cl₂ and to this solution there were added 38 mMoles of m-chloro-perbenzoic acid (80%) in 60 ml of CH₂ Cl₂, and the reaction mixture was stirred at 0° during 1 h. The formed acid was precipitated by the addition of gaseous NH₃. After filtration, and evaporation of the volatile fractions, the crude material was fractionally distilled under vacuum, and the distillate subjected to separation by column chromatography on SiO₂ (Merck 60; C), eluant: CHCl₃.

The isolated compound had the following physical data:

electronic ionization: m/e: 132 (41.8); 89 (42.5); 83 (41.4); 77 (23.1); 55 (100); 43 (16.7); 41 (38.6); 29 (19.2); 27 (18.4);

chemical ionization: (M+1)⁺ =177 (23); m/e: 161 (28); 145 (17); 133 (100); 117 (99); 115 (46.5); 99 (14.5); 83 (50.5);

IR: 2710, 1035 cm⁻¹ ;

NMR: (90 MHz; CDCl₃): 0.97 (3H, t); 1.68 (3H, d); 1.1 to 2.2 (6H, m); 2.67 (1H, broad band m); 3.62 (1H, m); 4.02 (1H, m); 4.1 (1H, q) δ ppm.

Due to the presence of an oxygen atom bonded to the cyclanic sulphur and the simultaneous presence of chirality centres in positions 2 and 4 of the ring, 2-methyl-4-propyl-1,3-oxathiane-3-oxide can occur not only in the form of a cis or trans cyclanic isomer relative to the substituents on the ring, but also as an axial or an equatorial isomer with regard to its sulphoxide bond.

The separation of these four isomers could be achieved as indicated above by careful fractional distillation followed by column chromatography on silica gel (eluant: CHCl₃). The isolated compounds showed the following analytical characteristics:

cis-equatorial: MS: M⁺ =160 (<1); m/e: 132 (52), 89 (52), 83 (40), 77 (23), 55 (100), 43 (68), 41 (53), 29 (65) IR (neat): 2960, 2920, 2860, 1460, 1100 cm⁻¹ ;

cis-axial: MS: M⁺ =160 (<1); m/e: 132 (64), 89 (62), 83 (49), 77 (28), 55 (100), 41 (46). IR (KBr): 2950, 2850, 1450, 1100 cm⁻¹ ;

trans-equatorial: MS: M⁺ =160 (<1); m/e: 132 (61), 89 (58), 83 (45), 77 (39), 55 (100), 41 (51). IR (neat): 2960, 2920, 2860, 1460, 1100, 1050 cm⁻¹ ;

trans-axial: MS: M⁺ =160 (<1); m/e: 132 (25), 89 (25), 83 (34), 55 (100), 43 (38), 41 (53). IR (neat): 2960, 2920, 2860, 1450, 1100, 1040 cm⁻¹.

The above described processes have been used for the preparation of the compounds listed in the Table. The temperatures are indicated in degrees centigrade and the abbreviations have the meaning common in the art.

The invention is illustrated by the following Examples.

EXAMPLE 1 Aromatization of foodstuffs A.

Two syrups of raspberry and black-currant type, respectively, were prepared by diluting 1 part by weight of commercial syrup with 4 and 9 parts by weight, respectively, of water. The beverages thus obtained were flavoured with a proportion of 0.50 ppm and 0.10 ppm, respectively, of 2-methyl-4-propyl-1,3-oxathiane.

The flavoured beverages were subjected to organoleptic evaluation by a panel of experienced tasters whose judgment was expressed as follows:

the flavoured raspberry syrup possessed an improved top note and an overall aroma which was fuller and fresher than that of the unflavoured syrup,

the flavoured black-currant syrup showed a fuller and a more natural taste than the unflavoured one. It possessed moreover a better defined green and woody note.

B.

A commercially available tomato juice possessing a bland taste was flavoured with 2-methyl-4-propyl-1,3-oxathiane by using it at a concentration of 0.10 ppm based on the total weight of the flavoured foodstuff. The tomato juice thus aromatized presented a more natural top note when compared to the unflavoured material. It possessed as well a fresher and more fruity character than the latter.

A coffee drink was prepared by dissolving 1 g of commercial spray-dried coffee in boiling water. The beverage was then flavoured by adding to it at a concentration of 0.025 ppm, based on the weight of the flavoured material, 2-methyl-4-propyl-1,3-oxathiane. The thus flavoured beverage possessed a fuller taste of coffee and showed a more marked pleasant smoky-woody character.

D

100 g of "American blend" tobacco were sprayed with 2 g of a 0.01% solution of 2-methyl-4-propyl-1,3-oxathiane in 95% ethanol, and the tobacco thus flavoured was used to manufacture cigarettes. As a control, cigarettes were also manufactured from the same tobacco sprayed with 95% ethanol alone. The smoke from the cigarettes was subjected to organoleptic evaluation by a panel of flavour experts, who unanimously stated that the smoke of the flavoured cigarettes possessed a more marked "tobacco" character and a more pleasant note as compared with the smoke of the control cigarettes.

EXAMPLE 2

A base flavouring composition of the "Tutti-Frutti" type was prepared by admixing the following ingredients (parts by weight):

    ______________________________________                                         Vanillin        50                                                             Amyl butyrate   20                                                             Benzyl acetate  50                                                             Ethyl acetate   100                                                            Orange oil      100                                                            Citral          120                                                            Benzyl alcohol  440                                                            Total           1000                                                           ______________________________________                                    

Two flavour compositions were then prepared by mixing the following ingredients (parts by weight):

    ______________________________________                                                          Flavour A                                                                              Flavour B                                                              (control)                                                                              (test)                                                ______________________________________                                         "Tutti-Frutti" base (as                                                        indicated above)   100       100                                               2-Methyl-4-propyl-1,3-oxathiane                                                at 0.1% in 95% ethanol                                                                            --         25                                               95% ethanol        900       875                                                                  1000      1000                                              ______________________________________                                    

Flavour compositions A and B were then individually subjected to an evaluation by dissolving them, at a concentration of 0.10% by weight, in a sugar syrup prepared by dissolving 650 g of sucrose in 1000 ml of water. The majority of the taste panel members stated that the syrup flavoured with composition B presented an improved top note as well as a more fruity and fuller character as compared with the syrup flavoured with composition A.

EXAMPLE 3

A commercial compote was flavoured with 2-methyl-4-propyl-1,3-oxathiane-3-oxide at a concentration of 5 ppm based on the weight of the flavoured material. The flavoured foodstuff was then subjected to an evaluation by a panel of experienced tasters who stated that its taste was greener and more fruity than that of the unflavoured material. It possessed moreover a character reminiscent of rhubarb or green berries.

B

A commercial black-currant juice was flavoured with the said oxathiane-oxide at a concentration of 2 ppm. It was found that the typical black-currant character was thus enhanced.

C

By proceeding in an analogous way, a rhubarb compote was flavoured by using the said oxathiane-oxide at a concentration level of 3 ppm. The characteristic note of rhubarb was thus reinforced.

D

A coffee drink was prepared by dissolving 1 g of commercial spray-dried coffee in boiling water. The beverage was then flavoured by adding to it at a concentration of 1 ppm, based on the weight of the flavoured material, 2-methyl-4-propyl-1,3-oxathiane-3-oxide. The thus flavoured beverage possessed a fuller and richer taste of coffee and showed a slightly fruity character, typical for certain coffee qualities.

E

100 g of "American blend" tobacco were flavoured as indicated in Example 1 D. by using 2-methyl-4-propyl-1,3-oxathiane-3-oxide at a concentration level of 10 ppm, based on the total weight of the flavoured tobacco. The smoke of the thus manufactured cigarettes had a fuller taste and aroma of tobacco.

EXAMPLE 4

A base flavouring composition of "black-currant" type was prepared by admixing the following ingredients (parts by weight):

    ______________________________________                                         Vanillin        50                                                             Ethyl maltol    10                                                             α-Ionone 10%*                                                                            10                                                             Amyl acetate    10                                                             Amyl butyrate   20                                                             Eugenol         20                                                             Buchu oil       20                                                             Ethyl butyrate  50                                                             Triacetin       810                                                            Total           1000                                                           ______________________________________                                          *in 95% ethanol                                                          

By using the above base composition, there were prepared two novel flavouring compositions by mixing the following ingredients (parts by weight):

    ______________________________________                                                          Flavour A                                                                              Flavour B                                                              (control)                                                                              (test)                                                ______________________________________                                         "Black-currant" base comp-                                                     osition (as indicated above)                                                                      100       100                                               2-Methyl-4-propyl-1,3-oxathiane                                                at 1% in 95% ethanol                                                                              --         20                                               95% ethanol        900       880                                                                  1000      1000                                              ______________________________________                                    

The two above compositions A and B were evaluated by tasting them in an acidulated sugar syrup vehicle as indicated in Example 2 at a concentration of 0.1% by weight. The syrup flavoured with composition B has a fresher and more natural flavour character than that flavoured with composition A. Its taste was analogous to that developed by black-currant fruits.

EXAMPLE 5

Two base flavouring compositions of "grape-fruit" type were prepared by mixing together the following ingredients (parts by weight):

    ______________________________________                                                          Flavour A                                                                              Flavour B                                                              (control)                                                                              (test)                                                ______________________________________                                         Grape-fruit oil    200       200                                               2-Methyl-4-propyl-1,3-oxathiane                                                at 0.1% in 95% ethanol                                                                            --         25                                               95% Ethanol        800       775                                                                  1000      1000                                              ______________________________________                                    

The above base compositions were tasted in an acidulated sugar syrup vehicle as indicated in Example 2. The foodstuff flavoured with composition B possessed a more marked "grape-fruit" character as well as a more juicy taste.

EXAMPLE 6

A base perfuming composition of "plum" type was prepared by mixing together the following ingredients (parts by weight):

    ______________________________________                                         2,6,6-Trimethyl-but-2-en-1-oyl-cyclohex-2-ene                                  at 10%*                   400                                                  1-(3,3-cyclohex-6-en-1-yl)-pent-4-en-1-one                                     at 1%*                    200                                                  Dodecalactone             150                                                  Decalactone               100                                                  Menthyl acetate           100                                                  Dimethyl-benzyl-carbinyl butyrate                                                                         50                                                  Total                     1000                                                 ______________________________________                                          *in diethyl phthalate                                                    

By adding to 970 g of the above composition 30 g of a 1% solution of 2-methyl-4-propyl-1,3-oxathiane in diethyl phtahlate, there was obtained a novel composition the note of which had a more natural, refreshing and fruity plum character as compared to the base composition.

EXAMPLE 7

A base perfuming composition of "Chypre" type was prepared by mixing the following ingredients (parts by weight):

    ______________________________________                                         Bergamot oil         250                                                       iso-Methylionone     60                                                        Synth. rose oil      60                                                        Synth. Jasmin oil    60                                                        Coumarin             50                                                        Oriental Sandel-wood oil                                                                            50                                                        Ylang oil            40                                                        Musc ketone          40                                                        Bourbon vetyver oil  40                                                        Styrax resinoil 50%* 30                                                        Absolute Oak-moss    30                                                        Dodecanal 1%*        30                                                        Hydroxycitronellal   30                                                        Synth. civet 10%*    30                                                        Labdanum resinoid 50%*                                                                              30                                                        Undecenal 10%*       20                                                        Musc ambrette        20                                                        Synth. rose absolute 20                                                        Synth. Jasmin absolute                                                                              20                                                        Patchouli            15                                                        Neroli Bigarade      15                                                        Methyl-nonylacetaldehyde 1%*                                                                        15                                                        Eugenol              15                                                        Orris concrete       10                                                        Tarragon             10                                                        Vanillin             10                                                        Total                1000                                                      ______________________________________                                          *in diethyl phthalate                                                    

By adding to 990 g of the above base composition, 10 g of a 10% solution of 2-methyl-4-propyl-1,3-oxathiane in diethyl phthalate, there was obtained a novel composition which possessed an improved diffusiveness and a top note with a more defined fruity character than the base composition.

EXAMPLE 8

A natural black-currant juice was flavoured by adding to it trans 2-methyl-4-propyl-1,3-oxathiane-equatorial 3-oxide at a concentration of 5 ppm by weight, based on the weight of the flavoured material. The thus flavoured beverage possessed a more fruity, woody taste which conferred a more natural character as compared to the unflavoured material; the odour of the flavoured beverage was somewhat greener.

B

A natural passion fruit juice was flavoured by adding to it trans 2-methyl-4-propyl-1,3-oxathiane-equatorial 3-oxide at a concentration of 2.5 ppm. The flavoured beverage possessed as compared to the natural juice an enhanced fruity note as well as a more juicy character.

C

A canned natural grape-fruit juice was flavoured by adding to it trans 2-methyl-4-propyl-1,3-oxathiane-equatorial 3-oxide at a concentration of 5 ppm. The flavoured beverage possessed, as compared to the natural juice, a fresher and more fruit pulp character.

D

An instant onion soup was prepared by dissolving a commercial grade soup powder into boiling water. The thus prepared foodstuff was flavoured by adding to it cis 2-methyl-4-propyl-1,3-oxathiane-equatorial 3-oxide at a concentration of 1 ppm. The taste of the flavoured soup had more body and presented a fresher onion and meaty character as compared to the unflavoured material.

The Examples given hereinabove shall not be construed to restrict the scope of the present invention in any matter. By replacing the effective ingredients indicated therein by another one of the compounds defined by formula (I), namely those listed in the Table, analogous effects were observed. In some cases, however, by their use a more defined sulphury taste developed in the materials to which they are added, thus limiting the extent of their applications. 

What is claimed is:
 1. A composition comprising a compound of formula (I): ##STR13## in which: (a) m and n stand for zero or 1, and each of symbols R¹ to R⁸ represents a hydrogen atom or a saturated or unsaturated, linear or branched alkyl radical containing from 1 to 11 carbon atoms, or(b) n stands for 1 and m represents zero or 1, each of symbols R¹, R², R³ and R⁴ have the above described meaning, R⁵ and R⁷ each represents hydrogen and R⁶ together with R⁸ and the carbon atoms carrying them, in positions 5 and 6 respectively, form a substituted or unsubstituted cyclopentane or cyclohexane ring, or (c) n stands for 1 and m represents zero or 1, each of symbols R¹, R³, R⁵, R⁶ and R⁷ represents hydrogen, R² represents a lower alkyl radical or hydrogen atom, R⁴ represents a para-substituted or unsubstituted phenyl or a substituted or unsubstituted cyclohexenyl radical, and R⁸ stands for a lower alkyl, or (d) n stands for 1 and m represents zero or 1, each of symbols R¹, R³, R⁵, R⁶ and R⁷ represents hydrogen, R² a p-substituted or unsubstituted phenyl or a substituted or unsubstituted cyclohexenyl radical, R⁴ represents a lower alkyl radical or a hydrogen atom, and R⁸ stands for a lower alkyl or a hydrogen;and a tobacco product.
 2. A composition according to claim 1, in which said compound of formula (I) is in the form of one of its epimers or enantiomers.
 3. A composition according to claim 1, in which said compound of formula (I) is in the form of a mixture of its epimers or enantiomers.
 4. A method for modifying, improving or enhancing the organoleptic properties of tobacco products which comprises adding thereto a small but effective amount of at least one compound of formula (I), as defined in claim
 1. 